JP2000079337A - Microcapsule and its manufacture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To adjust the fracture strength of a microcapsule by a method wherein the film body of a wall film of the microcapsule is composed of a transglutaminase denatured protein and at least one of a water-soluble polymer compound, water-insoluble particle, and a water-hardly-soluble particle is mixed in the film body, as a component. SOLUTION: For manufacturing a microcapsule which can be suitably used in various fields such as medicines and detergent, after a microcapsule having a wall film mainly composed of a native protein is prepared, the microcapsule is dipped in an aqueous solution containing a transglutaminase and electrolyte to effect a transglutaminase denaturing of the protein. The wall film of the microcapsule contains one or more kinds of wall film modifying agents selected from the group consisting of a water-soluble polymer compound, a water- insoluble particle, and a water-hardly-soluble particle, and as the water-soluble polymer compound, for example, agar, starch, and as the water-insoluble particle and water-hardly-soluble particle, for example, silicic acid anhydride, granite porphyry are cited.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a microcapsule and a method for producing the same, and more particularly, to a microcapsule which is hardly broken during storage and whose breaking strength is adjusted so as to be easily broken by pressure during use. The present invention relates to a capsule and a method for producing the capsule.

[0002]

2. Description of the Related Art Conventionally, various physiologically active substances, fragrances, etc. have been used in various fields such as foods and drinks, pharmaceuticals, quasi-drugs, cosmetics, feeds and detergents.
Encapsulation of enzymes and the like has been carried out, and as a film-forming substance for forming the wall film of such microcapsules, proteins such as gelatin have been used. In order to enhance heat resistance and safety to the human body, it has been proposed to use denatured proteins, for example, Japanese Patent Application Laid-Open No. 2-86641 discloses a capsule based on a transglutaminase-denatured protein, Japanese Patent Application Laid-Open No. 9-313154. Japanese Patent Application Laid-Open Publication No. H10-157, discloses a gelatin capsule in which a transglutaminase solution is brought into contact with the surface layer of a capsule body to form a protective layer containing transglutaminase on the surface layer of the capsule body.

[0003] However, in the case of the microcapsules in which the wall membrane proposed above is formed of a transglutaminase-denatured protein, the breaking strength of the capsules is so strong that the microcapsules are hardly broken when used and the core substance is not released. There was a problem that there is. In addition, when preparing microcapsules mainly composed of a transglutaminase-denatured protein as the main component of the wall membrane, contacting the hydrated microcapsules mainly containing the undenatured protein with the transglutaminase solution causes the wall membrane to swell and denature. There is a problem that the core substance is easily eluted therein, and it becomes difficult to prepare a microcapsule containing a transglutaminase-denatured protein as a main component of the wall membrane.

The present invention has been made in view of the above circumstances,
Even when the transglutaminase-denatured protein is contained as the main component of the wall membrane, the breaking strength is adjusted so that the wall membrane is easily broken by the pressure during use, and the food and drink, pharmaceuticals, quasi-drugs, cosmetics, An object of the present invention is to provide a microcapsule that can be suitably used for various applications in various fields such as feed and a detergent, and a method for producing a microcapsule that can suitably produce the microcapsule.

[0005]

Means for Solving the Problems and Embodiments of the Invention In order to achieve the above object, the present inventor has determined that even when a transglutaminase-denatured protein is mainly contained in the wall membrane of a microcapsule, the pressure at the time of use may be reduced. As a result of intensive studies to develop a technology for easily destroying capsules, the main body of the microcapsule wall membrane is a transglutaminase-denatured protein, which contains at least one of a water-soluble polymer compound, water-insoluble particles and hardly water-soluble particles. By compounding the above as a composite material, the composite material functions as a wall film modifier for reducing the breaking strength of the wall film,
It has been found that the breaking strength of the microcapsules is adjusted by this, and furthermore, as a result of intensive studies on the method for producing such microcapsules, the hydrated microcapsules containing a native protein as a main component of the wall membrane are prepared in an aqueous transglutaminase solution. In the case of denaturing the native protein by immersion in water, it was found that adding an electrolyte such as sodium sulfate to the aqueous solution of transglutaminase can prevent swelling of the wall membrane due to salting out action of the electrolyte, leading to the present invention. Was.

That is, according to the present invention, the wall membrane of the microcapsule mainly contains a transglutaminase-denatured protein, and one or more kinds selected from water-soluble polymer compounds, water-insoluble particles and water-insoluble particles. After preparing a microcapsule characterized by the fact that a wall film modifying agent is blended and the breaking strength of the capsule was adjusted, and a microcapsule having a wall film mainly composed of undenatured protein, A method for producing microcapsules, characterized in that the protein is transglutaminase-denatured by immersing the protein in an aqueous solution containing transglutaminase and an electrolyte.

Hereinafter, the present invention will be described in more detail.

[0008] The microcapsule of the present invention is obtained by adding at least one or more of a water-soluble polymer compound, water-insoluble particles and poorly water-soluble particles to a wall film mainly composed of a transglutaminase-denatured protein as a wall film modifier. By reducing the breaking strength of the wall film, thereby adjusting the breaking strength of the microcapsules, in the case of the microcapsules of the present invention, the structure is not particularly limited, for example, oil components, oil The core material composed of an oil phase containing a soluble component, a surfactant and the like may have an O / W single-core structure in which the wall film is coated. O dispersed in the wall membrane
/ W may have a multi-core structure, and may further comprise a W / O in which the oil phase in which a core substance (inner aqueous phase) comprising a water phase containing a water-soluble substance is dispersed is coated with the wall film. / W type structure may be adopted. Among these structures, the O / W single-core structure is more preferable in consideration of the release of the core substance and the reduction of the capsule strength. Considering that both the water-soluble substance and the oil-soluble substance can be encapsulated, those having the W / O / W type structure are more preferable.

Here, the microcapsules of the present invention are W /
In the case of having an O / W type structure, the water-soluble component contained in the internal aqueous phase is not particularly limited as long as it is water-soluble, and is appropriately selected depending on the use of the microcapsule. 104, Red 102, Green 3
And water-soluble dyes such as No. 4, Yellow No. 4, water-soluble vitamins, water-soluble polymer compounds, water-soluble fragrances, water-soluble enzymes, and the like. These may be used alone or in appropriate combinations of two or more. be able to. The amounts of these components can be appropriately selected depending on the use, structure, etc. of the microcapsules, but are preferably 0.01 to 30% (% by weight, hereinafter the same) based on the total amount of the microcapsules (water content, the same applies hereinafter). ), More preferably about 0.1 to 25%. If the amount of the water-soluble component is too small, the effect of the component may not be sufficiently obtained, and if it is too large, it may be difficult to prepare microcapsules having a W / O / W structure.

[0010] The oil component to be blended in the oil phase includes:
Depending on the type of microcapsules, foods and drinks, pharmaceuticals, quasi-drugs, cosmetics, feeds and detergents, hydrophobic oils and fats used in products in various fields such as detergents can be used. Specific examples of such oily components include vegetable oils such as olive oil, palm oil, coconut oil, olive squalane, jojoba oil, soybean oil, rice bran oil, cottonseed oil, corn oil, animal oils such as shark squalane, and mineral oils such as paraffin. And synthetic oils such as medium-chain triglyceride, isopropyl myristate, isopropyl palmitate, octyldodecyl myristate, and polysiloxane. These can be used alone or in combination of two or more. it can.

The amount of the oily component can be appropriately selected depending on the use of the microcapsules and the like, but is desirably 0 to 100%, preferably about 10 to 90% based on the total amount of the oil phase.

In the oil phase, particularly in the case of a W / O / W type structure, a surfactant is usually blended.
From the viewpoint of the purpose and purpose of the microcapsules, those capable of forming a W / O emulsion and capable of being eaten, drunk, applied to the skin and the like are suitably used. Glycerin higher fatty acid ester, polyglycerin higher fatty acid ester,
Polyglycerin-condensed ricinoleate and sucrose fatty acid polyester are preferably used. As higher glycerin fatty acid esters, glycerin and C6 to C2 are used.
Esters of 0, especially 8 to 18 fatty acids, and polyglycerol higher fatty acid esters include polyglycerol having a polymerization degree of glycerin of 2 to 12, especially 4 to 10 and 6 to 6 carbon atoms.
Esters of 20 and especially 8 to 18 fatty acids, polyglycerol condensed ricinoleate esters, the degree of polymerization of glycerin is 2 to 12, particularly 4 to 10 esters of polyglycerin and condensed ricinoleic acid, sucrose fatty acid polyester The ester composition of sucrose and a fatty acid having 6 to 20 carbon atoms, particularly 8 to 18 carbon atoms, is such that the monoester content is 40% or less and the di- or tri- or more ester composition is 60% or more.

As these compounds, more specifically,
As glycerin higher fatty acid esters, for example, monoglyceryl stearate, monoglyceryl oleate, monoglyceryl palmitate, etc., as polyglycerin higher fatty acid esters, for example, decaglycerin decastearate, hexaglycerin tristearate, hexaglycerin pentastearate Ester, tetraglycerin monostearate, tetraglycerin tristearate, tetraglycerin pentastearate, decaglycerin decaoleate, decaglycerin monocaprylate, hexaglycerin pentaoleate, tetraglycerin monooleate Polyglycerin-condensed ricinoleate, such as tetraglycerin pentaoleate, etc. As sucrose fatty acid polyesters, such as sucrose stearic acid polyester, sucrose palmitic acid polyester, sucrose oleic acid polyester, sucrose lauric acid polyester, sucrose behenic acid polyester, sucrose Examples thereof include erucic acid polyesters, and among these, polyglycerin condensed ricinoleate such as hexaglycerin condensed ricinoleate and tetraglycerin condensed ricinoleate are particularly preferably used. The above surfactants can be used alone or in an appropriate combination of two or more.
In the case of the present invention, it is preferable to appropriately select and use a surfactant other than the above surfactant.

The amount of the above surfactant can be appropriately selected depending on the kind and the like. In the case of the W / O / W type structure, 0.01 to 20%, preferably 0 to 20% of the total amount of the oil phase. About 1 to 15%, in the case of an O / W type structure, if necessary, preferably 0 to 10%,
More preferably, about 0 to 5% is suitable. If the amount is too small, the stability may deteriorate in the case of a W / O / W type structure. If the amount is too large, the viscosity of the oil phase may increase and the handleability may deteriorate.

An oil-soluble component can be optionally added to the above oil phase as long as the effects of the present invention are not impaired. The oil-soluble component is not particularly limited as long as it is oil-soluble. Although it is appropriately selected depending on the use of the microcapsule, examples thereof include oil-soluble vitamins such as carotene and lycopene, oil-soluble antioxidants, oil-soluble flavors, and highly unsaturated fatty acids.

When the above oil-soluble components are blended, the blending amount is an effective amount capable of exhibiting the function of each component, and is 0.01 to 100%, preferably 0.1 to 1%, based on the total amount of the oil phase.
About 00% is preferable. If the amount is too small, the effect of the compounding may not be obtained. In the case of the present invention, the oil phase may be composed of only the oil-soluble component.

The amount of the oil phase can be appropriately selected depending on the use and structure of the microcapsule.
In the case of the / O / W type structure, it is 1 to 65%, preferably about 3 to 45% with respect to the total amount of microcapsules, and in the case of the O / W type structure, it is 2 to 80%, preferably 4 About 70% is desirable. If the amount of the oil phase is too small, the effect of compounding the oil phase may not be sufficiently obtained, and if the amount is too large, it may be difficult to form microcapsules.

The wall membrane in the microcapsule of the present invention is mainly composed of a transglutaminase-denatured protein, and the protein species (undenatured protein) is gelled so as to form the wall membrane of the microcapsule, and The type of protein is not particularly limited as long as it is a protein capable of denaturing transglutaminase.Examples of such protein species include casein, sodium-caseinate, α-lactalbumin, β-lactoglobulin, egg white protein, yolk protein, and myoglobin. , Collagen, gelatin, soy 11S globulin, soy 7S
Globulin, gliadin, glutenin and the like can be mentioned, and these can be used alone or in an appropriate combination of two or more. In the case of the present invention, among these, gelatin and the like are particularly preferably used. Here, the transglutaminase-denatured protein of the present invention is obtained by denaturing the above-described undenatured protein with transglutaminase. In the case of the microcapsule of the present invention, the denaturation method is not particularly limited, but the production method described below is used. The transglutaminase used for denaturing proteins in the present invention is an enzyme that cross-links and polymerizes protein molecules, and is used for improving physical properties and adhesion of foods. Usually, commercially available ones can be used.

The amount of the transglutaminase-denatured protein is preferably 1 to 40%, more preferably about 5 to 20%, based on the total amount of the water-containing wall membrane. If the amount is too small, encapsulation may not be performed. If the amount is too large, the capsule may be too hard or difficult to encapsulate.

The wall film of the present invention further contains at least one or more wall film modifiers selected from water-soluble polymer compounds, water-insoluble particles and poorly water-soluble particles. For example, agar, gellan gum,
Sodium alginate, pullulan, starch, gum arabic, pectin, xanthan gum, locust bean gum, cod gum, guar gum, carrageenan, tamarind seed polysaccharide, soybean dietary fiber, and the like. Silicic acid, magnesium silicate, calcium carbonate, barley stone, white carbon, clay mineral, calcium sulfate, barium sulfate, zeolite, etc. can be mentioned, and these can be used alone or in combination of two or more. Can be.
In the case of the present invention, among these, agar, gum arabic, tara gum, tamarind seed polysaccharide, locust bean gum, guar gum, anhydrous silicic acid, magnesium silicate, calcium carbonate, malt stone, white carbon, clay mineral, calcium sulfate, Barium sulfate, zeolite and the like are preferably used.

The amount of the above-mentioned wall film modifier is not particularly limited, and is an amount which can be adjusted to a desired breaking strength for the wall film mainly composed of the above-mentioned transglutaminase-denatured protein. Glutaminase denatured protein: wall membrane modifier (weight ratio) = 1: 0.01 to 1:
1, preferably in the range of 1: 0.02 to 1: 0.5. If the mixing ratio of the wall film modifying agent is too large, encapsulation may be difficult, and if it is too small, it may be difficult to adjust the breaking strength of the target wall film. For the same reason, the compounding amount of the above-mentioned wall film modifying agent with respect to the total amount of the water-containing wall film is suitably in the range of 0.01 to 40%, preferably about 0.1 to 10%.

The microcapsule of the present invention is composed of the above-mentioned components. As described above, any one of the O / W single-core structure, the O / W multi-core structure and the W / O / W structure is used. In the case of microcapsule particles having an O / W single-core structure, the average particle size of the microcapsule particles is preferably in the range of 50 to 3000 μm, more preferably 100 to 2000 μm. If the average particle size is too small, handling of the capsule particles may be poor, and if too large, sufficient capsule strength may not be obtained. In this case, the average particle diameter of the core substance is preferably 20 to 2600 μm, more preferably 3 to 2600 μm.
The range is from 0 to 1600 μm. If the average particle size of the core material is outside the above range, the capsule strength may be insufficient. Further, for the same reason, the ratio between the average particle diameter of the core material and the average particle diameter of the microcapsule particles is as follows:
Preferably 1: 1.1 to 1: 3, more preferably 1:
It is about 1.2 to 1: 2.5.

In the case of microcapsule particles having an O / W multi-core structure, the average particle size of the microcapsule particles is preferably 50 to 3000 μm, more preferably 100 to 2000 μm, for the same reason. Is preferably in the range of 0.01 to 10 μm, more preferably 0.1 to 5 μm, and the ratio of the average particle diameter of the core substance to the average particle diameter of the microcapsule particles is preferably 1 : 5 to 1: 300,000, more preferably 1:20 to 1: 20,000.

In the case of microcapsule particles having a W / O / W type structure, the average particle diameter of the microcapsule particles is preferably 50 to 3000 μm for the same reason.
More preferably in the range of 100 to 2000 μm, the average particle size of the inner aqueous phase is preferably in the range of 0.01 to 10 μm, more preferably in the range of 0.1 to 5 μm, and the average particle size of the W / O particles is preferably 20 The average particle size of the internal aqueous phase, the average particle size of the W / O particles, and the average particle size of the microcapsule particles are preferably 1: 1. 8: 5-
1: 260,000: 300,000, more preferably 1: 9: 20 to 1: 16,000: 20,000.

The microcapsule of the present invention is prepared by blending the above-mentioned wall film modifier into the wall film so as to reduce the breaking strength of the wall film and to be easily broken by the pressure during use. The breaking strength of the wall film can be appropriately selected depending on the use of the microcapsule, etc.
When a load is applied at 25 ° C. and the load at which the capsule breaks is measured, the weight is desirably 1 to 700 g, preferably 5 to 300 g. If the breaking strength is too small, the capsule may be broken at the time of storage, blending into tablets, etc.,
If the size is too large, the capsule may be difficult to break during use, and the object of the present invention may not be achieved.

The method for producing a microcapsule of the present invention comprises:
Although not particularly limited, after preparing microcapsules having a wall membrane mainly composed of a native protein, the microcapsules are immersed in an aqueous solution containing transglutaminase and an electrolyte to transform the above-mentioned protein. The microcapsules can be suitably produced by the method for producing microcapsules of the present invention, which is characterized by performing glutaminase modification.

That is, the production method of the present invention firstly prepares a microcapsule having a wall membrane mainly composed of the above-mentioned protein species (native protein). In this case, the preparation method is not particularly limited. A known microencapsulation method can be adopted, for example, W / O / W
In the case of a microcapsule having a mold structure, the components of the internal aqueous phase are dissolved in water or hot water, and the oil phase components are previously heated to an appropriate temperature as needed and uniformly mixed and dissolved. The W / O emulsion is prepared by mixing and stirring with the mixed oil phase. Here, as the emulsifier, an azihomomixer, a kneader, a milder, or the like is used, and an azihomomixer is particularly preferable. The temperature conditions are as follows:
Although not particularly limited, it is necessary that the oil phase is molten. The stirring conditions are the same as those under the normal conditions of the above apparatus.
Stir for ~ 120 minutes. The mixing ratio of the internal water phase and the oil phase is preferably about 5:95 to 75:25 (internal water phase: oil phase).

Next, in any structure, each component of the wall membrane mainly composed of the above-mentioned native protein is dissolved in water or warm water in advance to prepare an aqueous phase for the wall membrane. , The concentration of the native protein in the aqueous phase for the wall membrane is 1 to 40.
%, Preferably 5 to 20%. If the concentration of the native protein is too low, encapsulation may not be performed, and if it is too high, the capsule may become hard or difficult to encapsulate.

Then, the W / O emulsion (W / O type emulsion)
The oil phase (in the case of the O / W type structure) or the oil phase (in the case of the O / W single core type structure) is fed to the inner nozzle of the double orifice, and the water phase for the wall film is fed to the outer nozzle. A capsule having a W / O / W type structure or an O / W single core type structure as shown in FIG. 2 or FIG. 1 is prepared. At this time, a capsule having a desired particle size can be prepared by giving vibration or rotation to the nozzle.
In the case of an O / W multi-core structure, an oil phase is emulsified in the water phase for a wall film to form an emulsion using the oil phase as a dispersoid. In addition, as an emulsifying machine, Ajihomo mixer,
A kneader, a milder and the like are used, and an azihomomixer is particularly preferable. Further, the temperature condition is not particularly limited, but it is preferable to prepare in a temperature range in which the above-mentioned native protein does not gel. Here, the above W / O
The mixing ratio of the emulsion or oil phase and the water phase for the wall film is W
/ O emulsion or oil phase: water phase for wall film = 2: 1 to 1
1:20, preferably about 1: 1 to 1:10.

Next, the W / O / W type emulsion or the oil phase is solidified by solidifying the W / O / W type structure, the O / W single core type capsule or the O / W type emulsion wall film aqueous phase. A microcapsule membrane containing the above-mentioned native protein as a core substance and a wall membrane modifier is formed. As a method for solidifying or forming and solidifying the microcapsule film, a known granulation method can be adopted. In the case of the present invention, a submerged curing method, a spray cooling method or a powder bed method is particularly preferable. .

In any case, the average particle size of the above-mentioned hydrated microcapsules is preferably 50 to 3000 μm, and more preferably about 100 to 2000 μm.

Transglutaminase denaturation of the thus obtained hydrous microcapsules of the undenatured protein is performed as follows.

First, an aqueous solution of transglutaminase that denatures (hardens) proteins is prepared. Here, the concentration of transglutaminase can be appropriately selected, but is preferably 0.001 to 1%, particularly preferably 0.005 to 0.5%. If the concentration is too low, the denaturation rate may be slow. If the concentration is too high, the effect of increasing the concentration may not be obtained, and the cost may increase. The production method of the present invention is to mix an electrolyte in the aqueous solution, as the electrolyte, for example, an inorganic alkali metal salt, an organic alkali metal salt and the like, preferably an inorganic alkali metal salt and the like can be suitably used, Specifically, as inorganic alkali metal salts, for example, alkali metal salts of inorganic acids such as sulfuric acid, sulfurous acid, phosphoric acid, metaphosphoric acid, boric acid, carbonic acid, iodic acid, nitric acid, nitrous acid, sodium chloride, potassium chloride, etc. Examples of the organic alkali metal salt include alkali metal salts of organic acids such as citric acid, tartaric acid, and acetic acid, and these can be used alone or in an appropriate combination of two or more.

More specifically, the alkali metal salts of the above-mentioned inorganic acids include, for example, sodium sulfate, potassium sulfate, sodium bisulfite, sodium sulfite, potassium bisulfite, potassium sulfite, potassium dihydrogen phosphate, dipotassium hydrogen phosphate. , Tripotassium phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, sodium metaphosphate, sodium borate, potassium bicarbonate, potassium carbonate, sodium bicarbonate, sodium carbonate, sodium potassium carbonate, iodine And potassium nitrate, sodium iodate, potassium nitrate, sodium nitrate, potassium nitrite, sodium nitrite and the like.

As the alkali metal salt of the organic acid, more specifically, for example, sodium citrate, potassium citrate, sodium hydrogen tartrate, potassium hydrogen tartrate, sodium tartrate, potassium tartrate, potassium acetate, sodium acetate and the like can be mentioned. . In the case of the present invention, among the above-mentioned electrolytes, sodium sulfate, sodium dihydrogen phosphate, sodium chloride and the like are particularly preferably used.

The blending amount of the above-mentioned electrolyte can be appropriately selected depending on the type of the electrolyte and the native protein and the content of the native protein in the wall membrane. In the case of performing, when the concentration of sodium sulfate in the aqueous solution is y%, and the concentration of gelatin (the amount blended in the wall film of the hydrous microcapsules) is x%,
A ratio satisfying y ≧ [(x + 2.9) /2.0] is preferable. If the amount of sodium sulfate is too small, the capsule may be easily broken during the modification treatment. For the same reason, the concentration of the electrolyte in the aqueous solution is 2 to
It is preferably 30%, especially 4 to 20%, and more preferably transglutaminase: electrolyte = 1: 2 to 1/30000, especially 1: 8 to 1: 4000.

Then, the undenatured protein capsule was placed in the aqueous solution of transglutaminase-electrolyte.
g of the microcapsules by adding 0.01 g to 5 g of the microcapsules and holding the mixture for 10 minutes to 10 days with stirring. it can. Here, the temperature at the time of curing (denaturing) treatment is 0 to 60 ° C, particularly 20 to 50 ° C.
C is preferred. If the temperature is too low, the transglutaminase-electrolyte aqueous solution may solidify or the denaturation rate may decrease, and if the temperature is too high, the transglutaminase may be inactivated. In addition, if transglutaminase is added to the aqueous phase containing the native protein and then the mylocapsule is converted into a wall film, it becomes difficult to prepare the capsule film.

In the method for producing microcapsules of the present invention, any microcapsules containing a transglutaminase-denatured protein as the main component of the wall film, for example, those not containing the above-mentioned wall film modifying agent are suitable. Can be manufactured.

The microcapsules of the present invention thus obtained can be used for desired purposes by dispersing them as they are, or dispersing them in an aqueous liquid, or mixing and dispersing them with powders composed of appropriate components. Further, for example, the above-mentioned hydrated microcapsule particles can be dried by reduced-pressure drying, ventilation drying, fluidized-bed drying or the like, preferably after reducing the water content in the microcapsules to 10% or less, and then formed into tablets and the like. .

The use of the microcapsules of the present invention is not particularly limited, and can be used for various purposes. For example, the microcapsules can be applied to skin, hair, etc. as pharmaceuticals, quasi-drugs, cosmetics, etc. When used as a cleaning agent, or as a food, health food, pharmaceutical product, etc. for food or drink, microcapsules are destroyed on the surface of the skin, the surface of the object to be cleaned, the body, etc., and core substances are released. It can exert various functions and is effective when used in these applications, and is particularly useful as a compounding agent for external preparations such as various pharmaceuticals, quasi-drugs, and cosmetics to be applied to skin, hair, etc. It is.

The microcapsules of the present invention are used in various applications as described above. For example, the microcapsules for various uses such as foods, health foods, pharmaceuticals, quasi-drugs, cosmetics, and detergents are used. It is suitable as an agent.

[0042]

The microcapsules of the present invention are prepared by adjusting the breaking strength of microcapsules mainly composed of a transglutaminase-denatured protein as a wall membrane. Can be obtained to obtain a microcapsule from which the core material and the like are released. Accordingly, the microcapsules are suitably used for various uses such as foods, health foods, pharmaceuticals, quasi-drugs, cosmetics, and detergents.

Further, the method for producing microcapsules of the present invention is characterized in that, in a microcapsule containing a native protein as a main component of the wall membrane, the native protein is denatured by transglutaminase without swelling or dehydration of the wall membrane. Therefore, it is possible to prepare microcapsules containing a transglutaminase-denatured protein as a main component of the wall membrane and whose breaking strength is adjusted by the wall membrane modifier.

[0044]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. The percentages in the table are% by weight.

[Examples 1 to 4 and Comparative Example 1] According to the composition shown in Table 1, a predetermined amount of red dye No. 104 and gelatin were dissolved in purified water at 60 ° C. using a stirrer to obtain a core substance (inner aqueous phase). ) Was prepared. Next, 20.0 parts by weight of the dye aqueous solution and an oil phase (cacao butter or corn oil 87.5% by weight, which had been prepared in advance to have the composition shown in Table 1,
Hexaglycerin condensed ricinoleate 12.5
80% by weight) and using a homomixer (Special Kika Co., Ltd.) at 10,000 rpm and 60 ° C.
After stirring for minutes, a W / O emulsion was prepared.

Only the W / O type emulsion or oil phase prepared by the above method is shown in Table 1 in the O / W ratio (weight) or (W / O
O) / W ratio (weight)) at the inner nozzle of the double orifice at 2.2 g / min, and at the outer nozzle 14.4 g / water phase prepared in advance for the wall membrane according to the composition of Table 1. Feed each minute, and 1800H into the double orifice
z (vibration temperature: 50 ° C.), and an O / W single-core structure (Examples 1 and 2) in which an oil phase 2 is covered with a wall film 3 as shown in FIG. Microcapsules having a W / O / W type structure (Examples 3, 4 and Comparative Example 1) in which an oil phase 2 in which a phase 1 is dispersed and covered with a wall film 3 are prepared, and a particle diameter of about 640 μm is prepared and stirred. In corn oil (about 15 ° C.), and the aqueous phase for wall membrane was cooled and solidified. After cooling, corn oil used as a dispersion medium was separated by suction filtration, and then washed with petroleum ether to prepare a red pigment unmodified gelatin film microcapsule.

The capsules obtained by the above method are immersed in a stirred aqueous solution of transglutaminase 0.02% by weight and 10% by weight of sodium sulfate at a ratio of capsule: aqueous solution (weight ratio) = 1: 9 for 4 hours. Then, the gelatin was modified (hardened). After curing, the transglutaminase-sodium sulfate aqueous solution was separated by suction filtration to prepare transglutaminase-modified gelatin membrane microcapsules of Examples 1 to 4 and Comparative Example 1. In addition, transglutaminase 0.02 containing no sodium sulfate was used.
When the unmodified gelatin membrane microcapsules of Example 1 were immersed in a 4% by weight aqueous solution for 4 hours in the same manner as described above, the wall membrane swelled, the capsules were broken, and elution of the core substance was observed.

Room temperature (20 to 25 ° C.) using a rheometer (manufactured by Fudo Kogyo Co., Ltd.) for each of the above hydrous microcapsules.
, And the breaking load (n = 10 average value) was measured to determine the breaking strength of each microcapsule. Table 1 shows the results
It is described together.

[0049]

[Table 1]

[Brief description of the drawings]

FIG. 1 is a schematic view showing the structure of a microcapsule before denaturation in an example of the present invention.

FIG. 2 is a schematic diagram showing the structure of a microcapsule before denaturation in Examples and Comparative Examples of the present invention.

[Brief description of reference numerals]

 1 internal water phase 2 oil phase 3 wall membrane

Continued on the front page (72) Inventor Emi Takagi 1-3-7 Honjo, Sumida-ku, Tokyo Inside Rion Co., Ltd. (72) Inventor Kentaro Takayama 1-3-7 Honjo, Sumida-ku, Tokyo Lion stock In-house F-term (reference) 4B035 LC03 LE07 LG15 LG51 LK14 LP36 4B048 PE10 PN04 4C076 AA64 DD24 DD46 EE42 EE60 FF22 FF23 FF36 GG22 4G005 AA01 AB09 AB14 AB15 AB17 BA11 BB04 BB13 BB19 BB25 DB12 DB05 DB12 EA01 EA02 EA03 EA05 EA07

Claims (2)

[Claims] 1. The microcapsule wall membrane mainly contains a transglutaminase-denatured protein,
A microcapsule characterized in that one or more wall film modifiers selected from a water-soluble polymer compound, water-insoluble particles and poorly water-soluble particles are blended to adjust the breaking strength of the capsule. 2. After preparing a microcapsule having a wall membrane mainly composed of an undenatured protein, the microcapsule is immersed in an aqueous solution containing transglutaminase and an electrolyte to perform transglutaminase denaturation of the protein. A method for producing microcapsules, characterized in that: